CN114069024A - 3D printing solid-state battery and preparation method and application thereof - Google Patents
3D printing solid-state battery and preparation method and application thereof Download PDFInfo
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- CN114069024A CN114069024A CN202111346444.7A CN202111346444A CN114069024A CN 114069024 A CN114069024 A CN 114069024A CN 202111346444 A CN202111346444 A CN 202111346444A CN 114069024 A CN114069024 A CN 114069024A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 23
- -1 polyoxyethylene Polymers 0.000 claims abstract description 23
- 239000006258 conductive agent Substances 0.000 claims abstract description 20
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- 239000002033 PVDF binder Substances 0.000 claims abstract description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 45
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
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- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a 3D printing solid-state battery and a preparation method and application thereof. The 3D printing solid-state battery comprises a positive pole piece, a negative pole piece and a solid electrolyte between the positive pole piece and the negative pole piece; the raw materials of the positive pole piece comprise, by mass, 70-80% of a positive active material, 5-10% of an electronic conductive agent, 2-10% of an ionic conductive agent, 2-4% of LiTFSI, 1.5-5% of polyvinylidene fluoride, 4-6% of polyethylene oxide and a positive solvent; the raw materials of the positive pole piece account for 20-50% of the solid content of the positive pole solvent. The invention adopts 3D printing technology to design the solid electrolyte with precise surface appearance and internal structure, improves the interface contact between the electrolyte and electrodes, improves the ion transfer between the electrodes and the electrolyte, and improves the lithium ion transmission between the anode and the solid electrolyte by combining with the polymer composite anode added with polyoxyethylene.
Description
Technical Field
The invention relates to the field of lithium ion batteries, and relates to a 3D printing solid-state battery and a preparation method and application thereof.
Background
In recent years, electrochemical energy storage has become the most widely used energy storage technology due to the increasing demand for energy. Among them, lithium ion batteries have become one of the focuses of research due to the characteristics of high energy density and long cycle life. With the continuous optimization of lithium ion battery technology, higher and higher demands are made on the energy density of lithium ion batteries. Due to the higher specific capacity and low electrochemical potential, the energy density can be theoretically improved by about 50% by using lithium metal instead of a graphite negative electrode. At present, the traditional lithium ion battery still adopts organic liquid electrolyte, although the ionic conductivity is high and the electrode wettability is good, the traditional lithium ion battery has the characteristics of flammability, explosiveness and easy leakage, and lithium dendrite is easy to generate to pierce a diaphragm to cause short circuit of the battery, so that the battery has great potential safety hazard. The safety problem becomes more pronounced if the battery uses a lithium metal negative electrode with a liquid electrolyte. Lithium metal itself is thermodynamically unstable in an organic electrolyte, and in addition, lithium ions acquire electrons from an external circuit during charging and then are directly deposited on the surface of or under the negative electrode in the form of metal-lithium particles, and dendrites more easily grow to cause short-circuiting of the battery, resulting in ignition and explosion, hindering further development of the lithium metal battery.
Therefore, in order to solve the safety problem of the lithium metal battery, the solid-state battery has a wide development prospect in the direction of the next generation lithium battery. Compared with liquid electrolyte, the solid electrolyte has the characteristics of no volatilization, difficult combustion, no liquid leakage, high structural stability and better safety performance. However, the liquid electrolyte can effectively wet the positive and negative electrode interfaces, but the interface impedance is increased due to the existence of a gap between the solid electrolyte and the electrodes, and the ionic conductivity of the solid electrolyte is low, which are major obstacles for the commercial application of the solid electrolyte. Therefore, development of a new electrolyte-electrode structure is advantageous for improvement of performance of solid electrolytes and practical application of solid batteries.
CN111584940A discloses a method for improving interface stability of a solid electrolyte and a metal cathode, which comprises spin-coating a precursor solution on the solid electrolyte after surface treatment, drying, placing in an inert atmosphere, sintering at 400-500 ℃ for 4-8 h, and generating an AIF interface modification layer on the interface of the solid electrolyte and the metal cathode. However, after the sintering process, the interface modification layer has the defect of untight adhesion with the metal cathode interface, so that the interface impedance is improved.
CN110518278A discloses a solid electrolyte with a negative electrode interface layer, a preparation method thereof, and a solid battery, wherein the surface of the solid electrolyte has a liquid metal alloy layer, the liquid metal alloy layer modifies and modifies the negative electrode interface where the solid electrolyte contacts with a lithium metal negative electrode, and after the solid electrolyte is assembled into the solid battery, the solid-solid phase compatibility between the lithium metal negative electrode and the solid electrolyte material interface can be improved by virtue of the transition effect of the liquid metal alloy layer, so as to reduce the interface resistance, but insufficient electrolyte addition amount can cause water jump at the later stage of the battery cycle, and excessive electrolyte amount can reduce the battery safety performance. And the solid electrolyte is difficult to be compatible with the electrolyte, and certain chemical reaction can occur when the solid electrolyte is contacted with the electrolyte, so that the scheme of adding the electrolyte can be only used as a transition scheme and can be replaced in long-term use.
CN108493483A discloses a solid electrolyte membrane cell layer structure interface processing method and a lithium cell structure, which includes the following steps: providing a solid electrolyte membrane; forming an electrode active material layer on the solid electrolyte membrane to form a pre-cell layer structure; and carrying out hot-pressing treatment on the pre-cell layer structure at a preset hot-pressing temperature and a preset pressing pressure, wherein the preset hot-pressing temperature and the preset pressing pressure are the critical temperature and the critical pressure at which the solid electrolyte membrane is changed from a solid phase to a mobile phase. However, under external pressure, rupture of the material and deterioration of electrical properties may occur, which are disadvantageous for long-term cycling of the battery.
How to prepare a solid-state battery with low interface impedance between an electrolyte and a pole piece and high ionic conductivity is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a solid-state battery prepared by combining a 3D printing solid-state electrolyte and a polymer composite positive electrode added with polyoxyethylene.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the present invention is to provide a 3D printing solid-state battery, where the 3D printing solid-state battery includes a positive electrode plate, a negative electrode plate, and a solid electrolyte between the positive electrode plate and the negative electrode plate.
The raw materials of the positive pole piece comprise, by mass, 70-80% of a positive active material, 5-10% of an electronic conductive agent, 2-10% of succinonitrile and 2-4% of LiTFSI21.5-5% of polyvinylidene fluoride, 4-6% of polyethylene oxide and a positive electrode solvent.
Wherein the mass fraction of the positive electrode active material may be 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, or the like, the mass fraction of the electron conductive agent may be 5%, 6%, 7%, 8%, 9%, 10%, or the like, the mass fraction of succinonitrile may be 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, or the like, wherein the mass fraction of polyvinylidene fluoride can be 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, etc., wherein the mass fraction of said polyethylene oxide may be 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5%, 5.2%, 5.4%, 5.6%, 5.8%, or 6%, etc., but are not limited to the recited values and other values not recited within the numerical range are equally applicable.
The raw material of the positive pole piece accounts for 20-50% of the solid content of the positive pole solvent, wherein the solid content can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48% or 50%, and the like, but the raw material is not limited to the recited numerical values, and other numerical values not recited in the numerical value range are also applicable.
The 3D printing solid-state battery can control the morphology structure of solid electrolyte: one of the main problems of the solid electrolyte is poor interface contact between the electrolyte and an electrode, and the solid electrolyte with precise surface appearance and internal structure can be designed by adopting a 3D printing technology to improve the interface contact between the electrolyte and the electrode; the 3D printed solid electrolyte can improve the ion transfer between the electrode and the electrolyte: the three-dimensional electrolyte manufactured by 3D printing has the characteristics of shorter ion transfer path and smaller resistance, the binder polyethylene oxide added in the positive pole piece is also beneficial to the lithium ion transmission between the positive pole piece and the solid electrolyte, and the energy density and the power density of the battery can be improved by combining the positive pole piece and the solid electrolyte to manufacture the high-performance battery.
As a preferred embodiment of the present invention, the raw material of the positive electrode active material includes any one or a combination of at least two of an NCM ternary material, an NCA ternary material, lithium iron phosphate, lithium manganate, lithium cobaltate, a binary metal sulfide, a sulfur oxide composite, a metal oxide composite, a sulfur composite, or a carbon composite, and typical but non-limiting examples of the combination include a combination of an NCM ternary material and an NCA ternary material, a combination of lithium iron phosphate and lithium manganate, a combination of lithium cobaltate and lithium iron phosphate, a combination of an NCA ternary material and lithium cobaltate, a combination of a binary metal sulfide and sulfur oxide composite, a combination of a metal oxide composite and a sulfur composite, or a combination of lithium cobaltate and a carbon composite, and the like.
Preferably, the electronic conductive agent comprises any one of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube or a combination of at least two of them, wherein typical but non-limiting examples of the combination are a combination of conductive carbon black and conductive graphite, a combination of conductive graphite and carbon fiber, a combination of carbon fiber and carbon nanotube or a combination of carbon nanotube and conductive carbon black, and the like.
Preferably, the ionic conductive agent comprises succinonitrile.
Preferably, the positive electrode solvent includes N-methylpyrrolidone.
A second object of the present invention is to provide a method for manufacturing a 3D printed solid-state battery according to the first object, the method comprising:
printing 3D printing ink on a substrate by using a 3D printer to obtain the solid electrolyte;
assembling the positive pole piece, the solid electrolyte and the negative pole piece into a battery cell, carrying out hot pressing treatment to obtain a solid battery cell, and loading the solid battery cell into a battery shell to obtain the 3D printing solid battery.
The substrate of the present invention includes any one of an aluminum foil, a copper foil, a PET film, or a PP film. The negative pole piece is a lithium metal negative pole piece.
According to the preferable technical scheme, the 3D printing ink comprises, by mass, 1-10% of an inorganic filler, 50-80% of an electrolyte, 1-40% of a polymer monomer, 0.5-1% of a thickener and 0.05-0.1% of an initiator.
Wherein the inorganic filler may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., the electrolyte may be 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, etc., the polymer monomer may be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, etc., the thickener may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc., the initiator may be 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical scheme of the invention, the inorganic filler comprises SiO2、Al2O3Any one or a combination of at least two of montmorillonite, LLZO, LATP, LAGP or LLTO, wherein a typical but non-limiting example of such a combination is SiO2And Al2O3Combination of (1) and Al2O3And a combination of montmorillonite, a combination of montmorillonite and LLZO, a combination of LLZO and LATP, a combination of LATP and LAGP, or a combination of LAGP and LLTO, and the like.
As a preferred embodiment of the present invention, the electrolyte includes an organic solvent, a lithium salt, and an additive.
Preferably, the organic solvent comprises any one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane or acetonitrile, or a combination of at least two thereof, wherein typical but non-limiting examples thereof are: a combination of ethylene carbonate and propylene carbonate, a combination of propylene carbonate and dimethyl carbonate, a combination of dimethyl carbonate and diethyl carbonate, a combination of diethyl carbonate and ethyl methyl carbonate, a combination of ethyl methyl carbonate and gamma-butyrolactone, a combination of gamma-butyrolactone and methyl formate, a combination of methyl formate and dimethoxymethane, or a combination of dimethoxymethane and acetonitrile, and the like.
Preferably, the lithium salt comprises any one of or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis (difluorosulfonimide), lithium bis (trifluoromethylsulfonyl imide), lithium bis (oxalato) borate, lithium difluorooxalato borate, or lithium bis (oxalato) borate, wherein typical but non-limiting examples of such combinations are: a combination of lithium hexafluorophosphate and lithium tetrafluoroborate, a combination of lithium tetrafluoroborate and lithium perchlorate, a combination of lithium perchlorate and lithium hexafluoroarsenate, a combination of lithium hexafluoroarsenate and lithium bis-difluorosulfonimide, a combination of lithium bis-difluorosulfonimide and lithium bis-trifluoromethylsulfonimide, a combination of lithium bis-trifluoromethylsulfonimide and lithium bis-oxalato-borate, a combination of lithium bis-oxalato-borate and lithium difluoro-oxalato-borate, or a combination of lithium fluoro-oxalato-borate and lithium bis-oxalato-borate, and the like.
Preferably, the lithium salt accounts for 5 to 15% of the electrolyte by mass fraction, wherein the mass fraction of the lithium salt may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the additive comprises any one of vinylene carbonate, fluoroethylene carbonate, cyclohexylbenzene, propylene sulfite or ethylene sulfate or a combination of at least two thereof, wherein typical but non-limiting examples thereof are: a combination of vinylene carbonate and fluoroethylene carbonate, a combination of fluoroethylene carbonate and cyclohexylbenzene, a combination of cyclohexylbenzene and propylene sulfite, or a combination of propylene sulfite and ethylene sulfate, and the like.
As a preferable embodiment of the present invention, the polymer monomer includes a monomer having an unsaturated bond and/or an easy-open ring cyclic monomer.
Preferably, the polymer monomer includes any one of acrylic acid, methacrylic acid, methyl methacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, acrylonitrile, ethylene carbonate, vinylene carbonate, ethylene oxide or 1, 3-dioxolane, or a combination of at least two thereof, wherein typical but non-limiting examples of the combination are a combination of acrylic acid and methacrylic acid, a combination of methacrylic acid and methyl methacrylate, a combination of methyl methacrylate and pentaerythritol tetraacrylate, a combination of pentaerythritol tetraacrylate and pentaerythritol triacrylate, a combination of pentaerythritol triacrylate and acrylonitrile, a combination of acrylonitrile and ethylene carbonate, a combination of ethylene carbonate and vinylene carbonate, a combination of vinylene carbonate and ethylene oxide or ethylene oxide and 1, combinations of 3-dioxolanes, and the like.
As a preferred technical scheme of the invention, the thickening agent comprises PMMA and/or polyethylene oxide.
Preferably, the initiator comprises any one or a combination of at least two of 1-hydroxycyclohexylphenylketone, 2-hydroxy-methylphenylpropane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin dimethyl ether, tolidine, 2-isopropylthioxanthone or 2, 4, 6- (trimethylbenzoyl) -diphenylphosphine oxide, typical but not limiting examples of such combinations are the combination of 1-hydroxycyclohexylphenylketone and 2-hydroxy-methylphenylpropane-1-one, the combination of 2-hydroxy-methylphenylpropane-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, and, A combination of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone and benzoin dimethyl ether, a combination of benzoin dimethyl ether and dibenzyl ketone, a combination of xylene ketone and 2-isopropyl thioxanthone, or a combination of 2-isopropyl thioxanthone and 2, 4, 6- (trimethylbenzoyl) -diphenylphosphine oxide, and the like.
The thickness of the solid electrolyte in the present invention is 5 to 20 μm, and the thickness may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, the hot press treatment temperature is 55 to 65 ℃, and the temperature may be 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the pressure of the hot pressing treatment is 0.3 to 0.5Mpa/pcs, wherein the pressure may be 0.3Mpa/pcs, 0.4Mpa/pcs, or 0.5Mpa/pcs, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the time of the hot pressing treatment is 20-40 min, wherein the time can be 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40min, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The invention also aims to provide application of the 3D printing solid-state battery, and the 3D printing solid-state battery is applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
(1) the solid-state battery utilizes a 3D printing technology, accurately controls the morphology structure of the solid-state electrolyte, and is beneficial to the customized production of the battery;
(2) the invention is suitable for lithium metal solid-state batteries, improves the lithium ion transmission between the electrode and the solid electrolyte, and has the ionic conductivity of 5 multiplied by 10-3S/cm；
(3) The preparation method of the solid-state battery is simple, saves the preparation time, reduces the raw material waste and reduces the cost.
Drawings
Fig. 1 is a flow chart of 3D printing of a solid electrolyte in examples 1 to 5 of the present invention and comparative examples 1 to 5.
Fig. 2 is a process flow diagram of 3D printed solid-state batteries in examples 1 to 5 of the present invention and comparative examples 1 to 5.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a 3D printing solid-state battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing 3.5 wt% of adhesive polyvinylidene fluoride, 5 wt% of polyethylene oxide and a positive electrode solvent N-methyl pyrrolidone to prepare a glue solution, rotating at 1000rpm, and stirring for 7.5 min. 75 wt% of lithium iron phosphate serving as a positive electrode active material, 7.5 wt% of conductive carbon black serving as an electronic conductive agent, 6 wt% of succinonitrile serving as an ionic conductive agent, 3% of lithium salt LiTFSI, the glue solution and the positive electrode solvent are mixed and stirred uniformly at the rotating speed of 1000rpm for 7.5min, and thus the positive electrode slurry with the solid content of 35% can be obtained. And then uniformly coating the positive electrode slurry on the two sides of an aluminum foil of a positive electrode current collector, wherein the thickness of the aluminum foil is 150 mu m, and drying, rolling, slitting and the like to obtain the required positive electrode piece.
(2) Preparation of 3D printing ink: weighing inorganic filler SiO according to mass ratio25 wt%, ethylene carbonate 70.40 wt%, LiPF63.53 wt% and 20 wt% of polymer monomer acrylic acid, and adding the materials into a closed container, performing ultrasonic treatment for 35min, and stirring for 8h to uniformly disperse the inorganic filler in other materials. Then, the thickening agent PMMA1 wt% was added to the above solution to control the solution viscosity at 13 mPas (55 ℃ C.). And finally, adding 0.07 wt% of 1-hydroxycyclohexyl phenyl ketone serving as an initiator, and continuously stirring for 6 hours to obtain the required 3D printing ink.
(3) Preparing a solid electrolyte: and 3D printing ink is filled into a needle cylinder, a needle head with the inner diameter of 350 mu m is selected, a layer of solid electrolyte with the thickness of 13 mu m is printed on the aluminum foil by using a 3D printer, and then drying treatment is carried out.
(4) Assembling the battery cell: the positive pole piece, the solid electrolyte and the lithium metal negative pole piece which are prepared in the process are prepared into a laminated core, and then a layer of diaphragm is wrapped outside the laminated core to fix the positive pole piece and the negative pole piece, so that the movement of the laminated core is prevented from generating short circuit. And obtaining the battery cell by tab welding, side sealing of the soft package battery, top sealing and pre-sealing.
(5) Electric core hot pressing: and (3) placing the battery cell in a hot press for hot pressing at 60 ℃, under the pressure of 0.4Mpa/pcs and for 30min, so that the solid electrolyte is tightly attached to the electrode, and the interface contact is enhanced. And (4) filling the battery core into a battery shell to prepare the solid battery. The flow of 3D printing the solid electrolyte is shown in fig. 1, and the flow of printing the solid battery is shown in fig. 2.
Example 2
The embodiment provides a preparation method of a 3D printing solid-state battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing 2 wt% of adhesive polyvinylidene fluoride, 4 wt% of polyethylene oxide and N-methyl pyrrolidone serving as a positive electrode solvent to prepare a glue solution, rotating at 800rpm, and stirring for 10 min. 70 wt% of lithium manganate serving as a positive electrode active material, 10 wt% of conductive graphite serving as an electronic conductive agent, 10 wt% of succinonitrile serving as an ionic conductive agent and 4% of lithium salt LiTFSI are uniformly mixed and stirred with the glue solution and the positive electrode solvent at the rotating speed of 800rpm for 10min, and thus the positive electrode slurry with the solid content of 20% can be obtained. And then uniformly coating the positive electrode slurry on the two sides of an aluminum foil of a positive electrode current collector, wherein the thickness of the aluminum foil is 100 mu m, and drying, rolling, slitting and the like to obtain the required positive electrode piece.
(2) Preparation of 3D printing ink: weighing inorganic filler Al according to mass ratio2O31 wt%, 72.72 wt% of electrolyte propylene carbonate and LiPF67.28 wt% of polymer monomer methacrylic acid 17.95 wt%, and adding the materials into a closed container, performing ultrasonic treatment for 10min, and stirring for 12h to uniformly disperse the inorganic filler in other materials. Then, 1 wt% of a thickener polyoxyethylene was added to the above solution to control the solution viscosity to 5 mPas (55 ℃ C.). And finally, adding 0.05 wt% of 2-hydroxy-methylphenyl propane-1-ketone serving as an initiator into the mixture, and continuously stirring the mixture for 4 hours to obtain the required 3D printing ink.
(3) Preparing a solid electrolyte: and (3) filling the 3D printing ink into a needle cylinder, selecting a needle head with the inner diameter of 200 mu m, printing a layer of solid electrolyte with the thickness of 5 mu m on the copper foil by using a 3D printer, and drying.
(4) Assembling the battery cell: the positive pole piece, the solid electrolyte and the lithium metal negative pole piece which are prepared in the process are prepared into a laminated core, and then a layer of diaphragm is wrapped outside the laminated core to fix the positive pole piece and the negative pole piece, so that the movement of the laminated core is prevented from generating short circuit. And obtaining the battery cell by tab welding, side sealing of the soft package battery, top sealing and pre-sealing.
(5) Electric core hot pressing: and (3) placing the battery cell in a hot press for hot pressing at 60 ℃, under the pressure of 0.4Mpa/pcs and for 20min, so that the solid electrolyte is tightly attached to the electrode, and the interface contact is enhanced. And (4) filling the battery core into a battery shell to prepare the solid battery. The flow of 3D printing the solid electrolyte is shown in fig. 1, and the flow of printing the solid battery is shown in fig. 2.
Example 3
The embodiment provides a preparation method of a 3D printing solid-state battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing 5 wt% of binder polyvinylidene fluoride, 6 wt% of polyethylene oxide and positive electrode solvent N-methyl pyrrolidone to prepare a glue solution, rotating at 1200rpm, and stirring for 5 min. 73 wt% of positive electrode active material lithium cobaltate, 10 wt% of electronic conductive agent carbon fiber, 2 wt% of ionic conductive agent succinonitrile, 4% of lithium salt LiTFSI, the glue solution and the positive electrode solvent are mixed and stirred uniformly at the rotation speed of 1200rpm for 5min, and then the positive electrode slurry with the solid content of 50% can be obtained. And then uniformly coating the slurry on the two sides of an aluminum foil of the positive current collector, wherein the thickness of the aluminum foil is 200 mu m, and obtaining the required positive pole piece through the steps of drying, rolling, slitting and the like.
(2) Preparation of 3D printing ink: weighing 8.9 wt% of inorganic filler montmorillonite, 47.6 wt% of electrolyte dimethyl carbonate and lithium salt LiBF according to mass ratio42.4 wt% of the inorganic filler and 40 wt% of polymer monomer methyl methacrylate, and adding the materials into a closed container, performing ultrasonic treatment for 60min, and stirring for 4h to uniformly disperse the inorganic filler in other materials. Then, 1 wt% of PMMA thickener was added to the above solution to control the solution viscosity to 20 mPas (55 ℃ C.). And finally, adding 0.1 wt% of initiator into the mixture, and continuing stirring for 8 hours to obtain the required 3D printing ink.
(3) Preparing a solid electrolyte: and 3D printing ink is filled into a needle cylinder, a needle head with the inner diameter of 500 mu m is selected, a layer of solid electrolyte with the thickness of 20 mu m is printed on the PET film by using a 3D printer, and then drying treatment is carried out.
(4) Assembling the battery cell: the positive pole piece, the solid electrolyte and the lithium metal negative pole piece which are prepared in the process are prepared into a laminated core, and then a layer of diaphragm is wrapped outside the laminated core to fix the positive pole piece and the negative pole piece, so that the movement of the laminated core is prevented from generating short circuit. And obtaining the battery cell by tab welding, side sealing of the soft package battery, top sealing and pre-sealing.
(5) Electric core hot pressing: and (3) placing the battery cell in a hot press for hot pressing at 60 ℃, under the pressure of 0.4Mpa/pcs and for 40min, so that the solid electrolyte is tightly attached to the electrode, and the interface contact is enhanced. And (4) filling the battery core into a battery shell to prepare the solid battery. The flow of 3D printing the solid electrolyte is shown in fig. 1, and the flow of printing the solid battery is shown in fig. 2.
Example 4
The embodiment provides a preparation method of a 3D printing solid-state battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing 2 wt% of binder polyvinylidene fluoride, 6 wt% of polyethylene oxide and positive electrode solvent N-methyl pyrrolidone to prepare a glue solution, rotating at 900rpm, and stirring for 8 min. 78 wt% of NCA ternary material serving as a positive electrode active material, 5 wt% of carbon nano tubes serving as an electronic conductive agent, 5 wt% of succinonitrile serving as an ionic conductive agent, 4% of lithium salt LiTFSI, the glue solution and the positive electrode solvent are mixed and stirred uniformly at the rotation speed of 900rpm for 8min, and then positive electrode slurry with the solid content of 30% can be obtained. And then uniformly coating the positive electrode slurry on the two sides of a positive electrode current collector, wherein the thickness of the positive electrode current collector is 130 mu m, and obtaining the required positive electrode piece through the steps of drying, rolling, slitting and the like.
(2) Preparation of 3D printing ink: weighing 2 wt% of inorganic filler LLZO, 42.8% of methyl ethyl carbonate electrolyte, 17.2% of lithium salt LiTFSI17.2% and 37% of polymer monomer pentaerythritol tetraacrylate according to the mass ratio, adding the materials into a closed container, carrying out ultrasonic treatment for 30min, and stirring for 10h to uniformly disperse the inorganic filler and print the ink in 3D. Then, 0.9 wt% of polyethylene oxide as a thickener was added to the above ink to control the solution viscosity to 9 mPas (55 ℃ C.). And finally, adding 0.1 wt% of benzoin dimethyl ether serving as an initiator, and continuously stirring for 5 hours to obtain the required 3D printing ink.
(3) Preparing a solid electrolyte: and (3) filling the 3D printing ink into a needle cylinder, selecting a needle head with the inner diameter of 280 mu m, printing a layer of solid electrolyte with the thickness of 10 mu m on the PP film by using a 3D printer, and drying.
(4) Assembling the battery cell: the positive pole piece, the solid electrolyte and the lithium metal negative pole piece which are prepared in the process are prepared into a laminated core, and then a layer of diaphragm is wrapped outside the laminated core to fix the positive pole piece and the negative pole piece, so that the movement of the laminated core is prevented from generating short circuit. And obtaining the battery cell by tab welding, side sealing of the soft package battery, top sealing and pre-sealing.
(5) Electric core hot pressing: and (3) placing the battery cell in a hot press for hot pressing at 60 ℃, under the pressure of 0.4Mpa/pcs and for 25min, so that the solid electrolyte is tightly attached to the electrode, and the interface contact is enhanced. And (4) filling the battery core into a battery shell to prepare the solid battery. The flow of 3D printing the solid electrolyte is shown in fig. 1, and the flow of printing the solid battery is shown in fig. 2.
Example 5
The embodiment provides a preparation method of a 3D printing solid-state battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing 4 wt% of binder polyvinylidene fluoride, 5 wt% of polyethylene oxide and positive electrode solvent N-methyl pyrrolidone to prepare a glue solution, rotating at 1000rpm, and stirring for 6 min. 71 wt% of positive active material lithium cobaltate, 8 wt% of electronic conductive agent carbon nano tube, 8 wt% of ionic conductive agent succinonitrile, and 4% of lithium salt LiTFSI, and the glue solution and the positive solvent are mixed and stirred uniformly at the rotating speed of 1000rpm for 6min, so that the positive slurry with the solid content of 40% can be obtained. And then uniformly coating the positive electrode slurry on the two sides of an aluminum foil of a positive electrode current collector, wherein the thickness of the aluminum foil is 170 micrometers, and drying, rolling, slitting and the like to obtain the required positive electrode piece.
(2) Preparation of 3D printing ink: weighing the inorganic filler LLTO8 wt%, the electrolyte propylene carbonate 63.63 wt% and the lithium salt LiBF according to the mass ratio46.37 wt% of polymer monomer pentaerythritol triacrylate and 21.12 wt% of the aboveAdding the materials into a closed container, performing ultrasonic treatment for 50min, and stirring for 10h to uniformly disperse the inorganic filler in other materials. Then, to the solution was added a thickener PMMA0.8 wt% to control the solution viscosity to 17 mPas (55 ℃ C.). And finally, adding 0.08 wt% of initiator of tolidine, and continuously stirring for 7 hours to obtain the required 3D printing ink.
(3) Preparing a solid electrolyte: and (3) filling the 3D printing ink into a needle cylinder, selecting a needle head with the inner diameter of 450 mu m, printing a layer of solid electrolyte with the thickness of 17 mu m on the aluminum foil by using a 3D printer, and drying.
(4) Assembling the battery cell: the positive pole piece, the solid electrolyte and the lithium metal negative pole piece which are prepared in the process are prepared into a laminated core, and then a layer of diaphragm is wrapped outside the laminated core to fix the positive pole piece and the negative pole piece, so that the movement of the laminated core is prevented from generating short circuit. And obtaining the battery cell by tab welding, side sealing of the soft package battery, top sealing and pre-sealing.
(5) Electric core hot pressing: and (3) placing the battery cell in a hot press for hot pressing at 60 ℃, under the pressure of 0.4Mpa/pcs and for 35min, so that the solid electrolyte is tightly attached to the electrode, and the interface contact is enhanced. And (4) filling the battery core into a battery shell to prepare the solid battery. The flow of 3D printing the solid electrolyte is shown in fig. 1, and the flow of printing the solid battery is shown in fig. 2.
Comparative example 1
This comparative example replaces the mass fraction of polyethylene oxide with 3%, and the other conditions are the same as in example 1.
Comparative example 2
This comparative example replaces the mass fraction of polyethylene oxide with 7%, and the other conditions are the same as in example 1.
Comparative example 3
This comparative example replaces the mass fraction of polyvinylidene fluoride with 1%, and the other conditions were the same as in example 1.
Comparative example 4
This comparative example replaces the mass fraction of polyvinylidene fluoride with 6%, and the other conditions were the same as in example 1.
Comparative example 5
This comparative example replaces polyethylene oxide with PMMA of the same mass, and the other conditions were the same as in example 1.
The 3D printed solid-state batteries in examples 1 to 5 and comparative examples 1 to 5 were tested at 25 ℃ cycling (0.2C/0.2C), and the results are shown in table 1.
TABLE 1
According to the results, the solid electrolyte can be prepared by using the 3D printing technology and assembled with the lithium metal and polymer composite positive electrode to form the solid battery. In a 25 ℃ cycle test, in example 1, compared with comparative example 5, the cycle number and the discharge specific capacity are greatly improved when the capacity retention rate is 80%, which indicates that the addition of polyoxyethylene to the positive electrode can improve the ion transmission between the pole piece and the solid electrolyte, thereby improving the cycle performance of the battery. It can be seen from example 1, ratio 1 and comparative example 2 that the battery performance is best when the polyoxyethylene content is 4 to 6%, and that too high or too low a polyoxyethylene content may hinder the battery performance. According to the embodiment 1, the proportion 3 and the comparative example 4, the battery performance is best when the content of the polyvinylidene fluoride is 1.5-5 wt%. Comparative examples 1-5, example 1, was best cycled when the polyethylene oxide content was 5% and the polyvinylidene fluoride content was 3.5%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A3D printing solid-state battery is characterized in that the 3D printing solid-state battery comprises a positive pole piece, a negative pole piece and a solid electrolyte between the positive pole piece and the negative pole piece;
the raw materials of the positive pole piece comprise, by mass, 70-80% of a positive active material, 5-10% of an electronic conductive agent, 2-10% of an ionic conductive agent, 2-4% of LiTFSI, 1.5-5% of polyvinylidene fluoride, 4-6% of polyethylene oxide and a positive solvent;
the raw materials of the positive pole piece account for 20-50% of the solid content of the positive pole solvent.
2. The solid-state battery according to claim 1, wherein the positive electrode active material includes any one of an NCM ternary material, an NCA ternary material, lithium iron phosphate, lithium manganate, lithium cobaltate, a binary metal sulfide, a sulfur oxide composite, a metal oxide composite, a sulfur composite, or a carbon composite, or a combination of at least two thereof;
preferably, the electronic conductive agent comprises any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube;
preferably, the ionic conductive agent comprises succinonitrile;
preferably, the positive electrode solvent includes N-methylpyrrolidone.
3. A method of manufacturing a 3D printed solid state battery according to claim 1 or 2, the method comprising:
printing 3D printing ink on a substrate by using a 3D printer to obtain the solid electrolyte;
assembling the positive pole piece, the solid electrolyte and the negative pole piece into a battery cell, carrying out hot pressing treatment to obtain a solid battery cell, and loading the solid battery cell into a battery shell to obtain the 3D printing solid battery.
4. The preparation method of claim 3, wherein the raw materials of the 3D printing ink comprise, by mass, 1-10% of the inorganic filler, 50-80% of the electrolyte, 1-40% of the polymer monomer, 0.5-1% of the thickener, and 0.05-0.1% of the initiator.
5. The method of claim 4Characterized in that the inorganic filler comprises SiO2、Al2O3Any one or a combination of at least two of montmorillonite, LLZO, LATP, LAGP or LLTO.
6. The production method according to claim 4 or 5, wherein the electrolytic solution includes an organic solvent, a lithium salt, and an additive;
preferably, the organic solvent comprises any one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane or acetonitrile or a combination of at least two of the above;
preferably, the lithium salt comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis (difluorosulfonimide), lithium bis (trifluoromethylsulfonyl imide), lithium bis (oxalato) borate, lithium difluoro (oxalato) borate or lithium bis (oxalato) borate;
preferably, the lithium salt accounts for 5-15% of the electrolyte by mass fraction;
preferably, the additive comprises any one of vinylene carbonate, fluoroethylene carbonate, cyclohexylbenzene, propylene sulfite or ethylene sulfate or a combination of at least two of the foregoing.
7. The production method according to any one of claims 4 to 6, wherein the polymer monomer comprises a monomer containing an unsaturated bond and/or an easy-open-ring cyclic monomer;
preferably, the polymer monomer includes any one of acrylic acid, methacrylic acid, methyl methacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, acrylonitrile, ethylene carbonate, vinylene carbonate, ethylene oxide, or 1, 3-dioxolane, or a combination of at least two thereof.
8. The production method according to any one of claims 4 to 7, wherein the thickener comprises PMMA and/or polyethylene oxide;
preferably, the initiator comprises any one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methylphenyl propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, benzoin dimethyl ether, tolidine, 2-isopropyl thioxanthone or 2, 4, 6- (trimethylbenzoyl) -diphenyl phosphine oxide or a combination of at least two of the above.
9. The preparation method according to any one of claims 3 to8, wherein the temperature of the hot pressing treatment is 55 to 65 ℃;
preferably, the pressure of the hot pressing treatment is 0.3-0.5 Mpa/pcs;
preferably, the time of the hot pressing treatment is 20-40 min.
10. Use of a 3D printed solid-state battery according to claim 1 or 2, characterized in that the 3D printed solid-state battery is used in the field of lithium ion batteries.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725498A (en) * | 2022-03-31 | 2022-07-08 | 中国地质大学（武汉） | Method for preparing PEO-MOF composite solid electrolyte based on 3D printing |
| CN117117293A (en) * | 2023-08-14 | 2023-11-24 | 合源锂创(苏州)新能源科技有限公司 | Electrode-electrolyte integrated assembly with three-dimensional structure and preparation process thereof |
| CN117154182A (en) * | 2023-10-30 | 2023-12-01 | 山东硅纳新材料科技有限公司 | Solid silicon-sulfur battery with gradually changed electrolyte components and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN108232111A (en) * | 2018-01-03 | 2018-06-29 | 清陶（昆山）能源发展有限公司 | A kind of anode composite pole piece of solid state battery and preparation method thereof |
| CN108963190A (en) * | 2017-05-19 | 2018-12-07 | 中国电子科技集团公司第十八研究所 | Method for preparing positive electrode for plastic crystal modified solid-state battery in situ |
| CN110518250A (en) * | 2019-09-06 | 2019-11-29 | 深圳先进技术研究院 | Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery |
| CN110571475A (en) * | 2019-08-12 | 2019-12-13 | 华中科技大学 | Method for preparing solid-state lithium ion battery through photocuring 3D printing |
| CN111129602A (en) * | 2019-12-20 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Preparation method of integrally-formed solid-state battery |
| CN111554972A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| CN111886090A (en) * | 2018-02-15 | 2020-11-03 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN112018430A (en) * | 2020-08-13 | 2020-12-01 | 浙江南都电源动力股份有限公司 | Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof |
| CN112234157A (en) * | 2020-09-25 | 2021-01-15 | 双登集团股份有限公司 | Composite positive pole piece for solid-state battery and preparation method thereof |
| CN112670483A (en) * | 2020-12-25 | 2021-04-16 | 合肥国轩高科动力能源有限公司 | Positive plate, positive polar plate and solid-state battery |
| CN113013414A (en) * | 2021-02-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Cobalt-free positive electrode slurry, preparation method thereof, positive plate and lithium ion battery |
| WO2021212428A1 (en) * | 2020-04-23 | 2021-10-28 | 宁德时代新能源科技股份有限公司 | Lithium metal battery and preparation method therefor, and apparatus comprising lithium metal battery and negative electrode plate |
-
2021
- 2021-11-15 CN CN202111346444.7A patent/CN114069024A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963190A (en) * | 2017-05-19 | 2018-12-07 | 中国电子科技集团公司第十八研究所 | Method for preparing positive electrode for plastic crystal modified solid-state battery in situ |
| CN108232111A (en) * | 2018-01-03 | 2018-06-29 | 清陶（昆山）能源发展有限公司 | A kind of anode composite pole piece of solid state battery and preparation method thereof |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN111886090A (en) * | 2018-02-15 | 2020-11-03 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN110571475A (en) * | 2019-08-12 | 2019-12-13 | 华中科技大学 | Method for preparing solid-state lithium ion battery through photocuring 3D printing |
| CN110518250A (en) * | 2019-09-06 | 2019-11-29 | 深圳先进技术研究院 | Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery |
| CN111129602A (en) * | 2019-12-20 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Preparation method of integrally-formed solid-state battery |
| WO2021212428A1 (en) * | 2020-04-23 | 2021-10-28 | 宁德时代新能源科技股份有限公司 | Lithium metal battery and preparation method therefor, and apparatus comprising lithium metal battery and negative electrode plate |
| CN111554972A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| CN112018430A (en) * | 2020-08-13 | 2020-12-01 | 浙江南都电源动力股份有限公司 | Composite solid electrolyte prepared based on in-situ thermal polymerization method and preparation method and application thereof |
| CN112234157A (en) * | 2020-09-25 | 2021-01-15 | 双登集团股份有限公司 | Composite positive pole piece for solid-state battery and preparation method thereof |
| CN112670483A (en) * | 2020-12-25 | 2021-04-16 | 合肥国轩高科动力能源有限公司 | Positive plate, positive polar plate and solid-state battery |
| CN113013414A (en) * | 2021-02-26 | 2021-06-22 | 蜂巢能源科技有限公司 | Cobalt-free positive electrode slurry, preparation method thereof, positive plate and lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725498A (en) * | 2022-03-31 | 2022-07-08 | 中国地质大学（武汉） | Method for preparing PEO-MOF composite solid electrolyte based on 3D printing |
| CN117117293A (en) * | 2023-08-14 | 2023-11-24 | 合源锂创(苏州)新能源科技有限公司 | Electrode-electrolyte integrated assembly with three-dimensional structure and preparation process thereof |
| CN117154182A (en) * | 2023-10-30 | 2023-12-01 | 山东硅纳新材料科技有限公司 | Solid silicon-sulfur battery with gradually changed electrolyte components and preparation method and application thereof |
| CN117154182B (en) * | 2023-10-30 | 2024-01-16 | 山东硅纳新材料科技有限公司 | Solid silicon-sulfur battery with gradually changed electrolyte components and preparation method and application thereof |
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